This invention relates to phenethyl alkyl and alkenyl ethers and to the uses thereof in combatting insects as a result of the discovery that the alkyl and alkenyl phenylethers are tobacco beetle pheromones or ectohormones; and in addition to the uses of phenethyl alkyl or alkenyl ethers in augmenting or enhancing the aromas of perfumes, colognes and perfumed articles (e.g., solid or liquid anionic, cationic, nonionic and zwitterionic detergents, fabric softeners, fabric softener articles, hair conditioners, odorants and deodorants). Obviously then, the invention also relates to one or more pleasant smelling pheromones or ectohormones useful for combatting insects yet, at the same time, not repulsive to the individual or group of individuals applying the pheromone or ectohormone to the area where the insects are to be combatted.
Pheromones or ectohormones are secreted by insects as so called socially active ingredients, e.g., as sexual attractants or aggregation substances. The use of these pheromones or ectohormones is known to attract insects into certain small sections of a contaminated area, to concentrate them in this are and then to destroy the insects in any known way, e.g., mechanically, chemically or with insecticides. This method leads to a very economical and concentrated use of the actual insecticides, especially of insecticides which are ecologically dangerous, whereby the spraying of large parts of the contaminated area in an expensive way, e.g., by spraying insecticides with an aeroplane, is avoided.
No pheromones have been discovered up to the present time for use with Lasioderma serricorne (F.) with the exception of cyclohexyl phenethylethers as described in co-pending application for U.S. patent, Ser. No. 192,238 now U.S. Pat. No. 4,306,096. Thus, the pheromones known up to the present time with the exception of the cyclohexyl phenethylethers of application for U.S. patent, Ser. No. 192,238 belong to a large variety of chemical substances and are, as a rule, effective only with respect to certain insects such as, for example, for use in combatting insects of the order coleoptera and the finally scolytidae and platypodidae which beetles cause substantial damage to forests and to the wood of trees generally as taught in U.S. Pat. No. 3,927,207 issued on Dec. 16, 1975.
Another problem as yet unsolved by the prior art with the exception of the use of cyclohexyl phenethylethers as described in application for U.S. patent, Ser. No. 192,238 concerns the utilization, either in conjuction with or as pheromones or ectohormones for insect attractants, of fragrance imparting, augmenting or enhancing agents. Such fragrance imparting, augmenting or enhancing agents must be either identical to or, at the very least, compatible with the pheromones or ectohormones. Previously such pheromones or ectohormones having their own aroma profiles have been found to have an aroma profile which either was esthetically displeasing or, at the very best, incapable of covering or deodorizing the chemical-like sharp, abrasive aroma of the insecticides used against the insects; that is, prior to the finding of the cyclohexyl phenethylethers of application for U.S. patent, Ser. No. 192,238, filed on Sept. 30, 1980.
An optimal solution to the foregoing problems would be to create, in one chemical, a pheromone or ectohormone; an insecticide; and an aroma augmenting or enhancing substance which is compatible with said pheromone or ectohormone and with said insecticide.
Notwithstanding the aforementioned pheromone or ectohormone properties and notwithstanding the aforementioned insecticide properties, chemical compounds which can provide green, fruity, floral, hyacinth-like, rosy, rose-hyacinth-like, galbanum-like, cassis-like and narcissus-like aromas with hyacinth/honey aroma on dry-out and with peppery and mushroom undertones which are both rich and full-bodied as well as long-lasting are desirable in the art of perfumery. Many of the natural materials which provide such fragrances and contribute such desired nuances to perfumery compositions are high in cost, unattainable at times, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is, accordingly, a continuing effort to find synthetic materials which will replace, enhance or augment the fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the compositions. The search for materials which can provide more refined, more natural-like, more long-lasting green, fruity, floral, hyacinth-like, rosy, rose-hyacinth-like, galbanum, cassis-like and narcissus-like aromas with hyacinth/honey aromas on dry-out and peppery and mushroom undertones has been difficult and relatively costly in the areas of both natural products and synthetic products.
Arctander in "Perfume and Flavor Chemicals (Aroma chemicals)", Volume II, 1969 describes phenylethyl alcohol as having a rose aroma.
The use in perfumery of alkyl ethers of phenylethyl alcohol is known. Thus, Chem. Abstracts, Volume 79, 1973, 18356m abstracts U.S. Pat. No. 3,734,970 which discloses the use of phenylethyl alcohol methylether having the structure: ##STR2## in perfumery. It is further indicated that this material is produced by reaction of phenylethyl alcohol with a mercury-aluminum couple to form triphenylethoxy aluminum and reacting the triphenylethoxy aluminum with dimethoxysulfoxide to form the phenylethyl alcohol methylether.
Chem. Abstracts, Volume 87, 1977, 87:135063q discloses the genus of compounds having the structure: ##STR3## which abstracts Japanese Kokai No. 77-07,911 and uses of these compounds in perfumery wherein R represents alkyl, alkenyl, alkynyl, aryl, aralkyl and cycloalkyl and R.sup.1 represents hydrogen or R and R.sup.2 represents alkyl or phenylalkyl.
Chem. Abstracts 90:127414, Volume 90 (1979) abstracts French Demande No. 2,373,276 which discloses the use of the compound having the structure: ##STR4## synthesized according to the reaction sequence: ##STR5## in perfumery particularly as a lilac perfumant.
Nothing in the prior art, however, discloses the specific compounds having the structures defined according to the genus: ##STR6## wherein R is C.sub.3 or C.sub.6 2.degree.-alkyl or C.sub.4 alkenyl.
Phenylethyl alcohol isoamylether has been used for several years in the perfumery industry but has been found to have an undesirable "chocolate" nuance. Phenylethyl alcohol isoamylether has the structure: ##STR7## and is a "primary" alkyl ether rather than a "secondary" alkyl ether.
Isobutyl phenylacetate (otherwise known as "Anther") having the structure: ##STR8## an ester, is described by Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)" 1969 as being extensively useful in perfumery for fresh "petal" notes in rose, peony, narcisse, carnation, sweet pea, freesia and hyacinth. Arctander also indicates that this material is on a "GRAS" list as having number 2210.
Arctander also indicates at monograph number 514 that isobutyl phenylether having the structure: ##STR9## has a harsh chemical odor, sweet but with a metallic chemical background and being remotely reminiscent of anise.
Phenethyl propionate has been disclosed in the Journal of Economic Entomology, 66, (5), 1973, and has been indicated by McGovern et al to be an attractant for Popillia japonica Newman (Japanese beetles) particularly in combination with eugenol. Indeed, in that same paper by McGovern et al., it is indicated that trans-2-hexanal, a well-known perfume ingredient, is also a Japanese beetle attractant. The phenethyl propionate has the structure: ##STR10##
In another paper by McGovern et al., Journal of Economic Entomology, Volume 63, Number 1, page 276, it is indicated that methyl cyclohexanepropionate and certain related chemicals are also attractants for Popillia japonica Newman.
Research concerning Lasioderma serricorne (F.) and attractants therefor are limited to the use of extracts of natural food odors. Thus, the paper by Fletcher and Garrett entitled "Ovipositional Response of Three Strains of the Cigarette Beetle to Extracts of Food Odors" in Tobacco International, 182 (5), pages 166-169, Mar. 7, 1980. Fletcher and Garrett disclose that the ovipositional response of three strains of the cigarette beetle is a function of different food odor attractants.
Nothing in the prior art, however, discloses the unexpected, unobvious and advantageous properties of the phenethylether derivatives having the generic structure: ##STR11## wherein R represents C.sub.3 or C.sub.6 2.degree.-alkyl or C.sub.4 alkenyl which are not only useful per se for augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles, but are also useful individually or taken in combination as Lasioderma serricorne (F.) pheromones and, in addition, as Lasioderma serricorne (F.) insecticides.